US3598741A - Acid compound for metal surface - Google Patents

Acid compound for metal surface Download PDF

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Publication number
US3598741A
US3598741A US864535A US3598741DA US3598741A US 3598741 A US3598741 A US 3598741A US 864535 A US864535 A US 864535A US 3598741D A US3598741D A US 3598741DA US 3598741 A US3598741 A US 3598741A
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acid
composition
magnesium
viscosity
concentration
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Shozo Kanno
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Chugai Kasei Co Ltd
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Chugai Kasei Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/08Acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/34Organic compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/16Acidic compositions
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/025Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes

Definitions

  • compositions having suitable viscosities for the cleaning and etching of metals comprising hydrofluoric acid, magnesium and at least one acid or salt of an acid selected from the group consisting of nitric acid, phosphoric acid, sulfuric acid and sulfonic acid.
  • This invention relates to an acidic composition for cleaning and for etching of metal. More particularly, it relates to an acidic chemical composition for the cleaning and etching of metal which has a desired viscosity making it possible to apply the same by means of a brush, by flowing or by spraying. Even more particularly, the invention relates to acidic compositions or compounds containing hydrofluoric acid, magnesium and at least one other acid or salt, as defined hereinbelow.
  • cleaning as used in this application is defined as the removal of scales, rust, corrosion, oxidation substances, stains and other deposits, which are nonmetallic substances, from metal surfaces, thereby exposing the bare metal surface.
  • the chemical mixtures employed in the present invention can be referred to as an acid compound, but this expression should not be taken to mean chemical compound in the ordinary sense of the term but, rather, a specific substance prepared by blending or mixing together several chemical substances. Since the resultant mixture does not necessarily form a single chemical compound, but constitutes a blend having a hybrid character of the mixture and the respective chemical components thereof, it will be referred to hereinafter as a composition.
  • compositions containing hydrofluoric acid for use on metal surfaces have been conventionally used in the art for cleaning considerably firm scales, oxide films and the like off the surface of metals such as stainless steel, heatresisting steels, titanium or aluminum. These compositions, containing hydrofluoric acid, are also effective in cleaning scales or oxide films off the surfaces of other metals, wherein compositions that do not contain hydrofluoric acid are substantially ineffective.
  • Some viscosity-increasing additives have been used in conventional cleaning compositions in order to attain the appropriate viscosity because it was not possible to attain such a viscosity by components having a cleaning function only.
  • Various kinds of high molecular weight substances such as cellulose derivatives, for example, starch, agaragar, carboxymethylcellulose or hydroxymethylcellulose, or inorganic substances, for example, diatomaceous earth, various clays or bentonite, have been conventionally used as additives.
  • viscosity-increasing additives organic substances are apt to be hydrolyzed in an acid solution, thereby decreasing their molecular Weights and hence decreasing the viscosity of the composition. This is particularly true of the carbohydrate additives. Even hydroxypropyl methylcellulose, which is believed to be highly resistant to the acids, is hydrolyzed with the passage of time, with the result that its viscosity is lost in a few days.
  • conventionally used inorganic viscosity-increasing additives which primarily comprise silicic acid and, additionally, include aluminum oxide or another component, have been used in compositions containing ordinary acids. However, these inorganic additives dissolve in a composition comprising hydrofluoric acid, resulting in losing the cleaning function of the acid as well as in increasing the viscosity through a formation of hydrosilicofluoric acid and of aluminum oxide.
  • the present inventor has conducted much research in order to overcome the above problems concerning the production of an acidic composition for cleaning or etching metal surfaces comprising hydrofluoric acid and which has a necessary and desired viscosity. As a result, it has become possible to overcome the above-mentioned problems without deteriorating the cleaning function of the composition.
  • one of the objects of the present invention is to provide acidic cleaning compositions for metals which overcomes the disadvantages and deficiencies of the prior art materials.
  • Another object of the present invention is to provide acidic compositions of the type described which have a suitable viscosity while maintaining a good cleaning or etching action.
  • a further object of the invention is to provide cleaning compositions for metal surfaces which contain hydrofluoric acid.
  • a still further object of the invention is to provide hydrofluoric acid-containing cleaning or etching agents for metal surfaces which can be applied by brushing, by flowing, by spraying, by immersing or as desired because of the suitable viscosity thereof.
  • an acidic composition comprising hydrofluoric acid, magnesium and at least one other additive selected from the group consisting of nitric acid, phosphoric acid, sulfuric acid and sulfonic acids having the chemical formula XSO H, wherein X is an aryl radical, an alkaryl radical or an alkyl radical.
  • Said acids include not only the free acid but also suitable salts thereof, particularly the inorganic salts.
  • the magnesium employed in the compositions of the invention is obtained from sources such as metallic magnesium and magnesium salts, for example, magnesium oxide, magnesium carbonate, magnesium nitride, magnesium phosphate, magnesium sulfate and magnesium salts of said sulfonic acids. Therefore, in this application, the term magnesium is used to include magnesium salts of this type.
  • hydrofluoric acid, the nitric acid, the phosphoric acid, the sulfuric acid, the sulfonic acid or their salts contained in the composition is provided in the form of the free acid, a magnesium salt thereof or from any other salt which can impart the acid radical of these acids through hydrolysis in an acid solution. Therefore, terms such as hydrofluoric acid, nitric acid, phosphoric acid, sulfuric acid and sulfonic acid are used in this application to include the suitable respective salts thereof.
  • sulfonic acid aryl sulfonic acids or alkaryl sulfonic acids can be employed.
  • examples thereof include benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, ethylbenzene-sulfonic acid, or propylbenzene-sulfonic acid.
  • Dodecylbenzenesulfonic acid having 12 carbon atoms in the alkyl radical thereof is preferred, because it is readily available and effects a good performance.
  • Propylnaphthalene-sulfonic acid, butylnaphthalene-sulfonic acid, eicosylbenzene-sulfonic acid, etc. can also be employed as the sulfonic acid component.
  • Groups containing 28 or less carbon atoms are preferable as the aryl radical or alkaryl radical contained in the sulfonic acid.
  • Sulfonic acid radicals containing 26 or less carbon atoms are even more preferable as effecting a sufficient dispersion.
  • Sulfonic acid radicals containing 29 or more carbon atoms are not preferred because of poor dispersion properties.
  • Alkylsulfonic acids which may be employed include, for example, decanesulfonic acid, hexadecanesulfonic acid, octadecanesulfonic acid, docosanesulfonic acid, hexacosanesulfonic acid, etc.
  • acids having alkyl radicals containing from 6 to 30 carbon atoms are preferred. When the number of carbon atoms is less than 6, the viscosity-increasing effect is low, and when the carbon number exceeds 30, an acceptable dispersion cannot be obtained.
  • the hydrofluoric acid is added to the composition of the invention principally for obtaining a cleaning and etching effect, rather than for obtaining a viscosity-increasing effect.
  • the hydrofluoric acid has a considerable effect in increasing the viscosity, the desired viscosity is really obtained by means of the other components.
  • the degree of concentration of the components in the composition of the invention can be selected in a wide range.
  • the concentration of hydrofluoric acid should be from about 1% to about 65% by weight of the resultant composition. At a concentration of hydrofluoric acid of less than about 1%, the function of cleaning or etching by the composition is not suflicient. At a concentration of more than about 65%, the volatility of the hydrofluoric acid is too high, making the handling of the cleaning or etching composition dangerous.
  • the viscosity can be increased by adding the magnesium to the composition in a certain proportion with respect to the amount of component acids.
  • the maximum viscosity can be attained at the proportion between amounts of the component acids and the magnesium when they are almost equivalent chemically to form magnesium salts of such acids, and especially acid salts thereof.
  • the amount of magnesium should be limited to the lowest possible value for obtaining a desired viscosity, because it is preferred to keep the amount of added magnesium as small as possible in order to obtain a high concentration of free acids, i.e., active acids which are effective for cleaning or etching metals.
  • the concentration of magnesium preferably ranges from about 0.1% to about 20% by weight. At a concentration of magnesium of less than about 0.1%, the viscosity-increasing effect cannot be obtained.
  • the composition is solid and a fluidity or plasticity cannot be obtained.
  • One, two or more acids selected from the group consisting of nitric acid, phosphoric acid, sulfuric acid and sulfonic acids are added to the composition and have the effect of increasing the viscosity of the composition cooperatively with the hydrofluoric acid and magnesium.
  • Any acid selected from the above group is capable of increasing the viscosity of the composition by the addition of only a small amount, and greater additions in crease the viscosity thereof.
  • the maximum viscosity can be obtained when the amount of component acids is approximately equivalent chemically with respect to the magnesium to form magnesium salts of these acids, and especially acid salts thereof.
  • Acids selected from the above-listed group give a stable viscosity to the composition. When contained therein, said acids have a cooperative and complementary effect in increasing the viscosity.
  • the sulfonic acid is added to the composition in a wide quantitative range without interfering with the performance of the cleaning or etching effect and, therefore, a desired viscosity of the composition can be obtained while retaining the cleaning or etching effect provided by the composition with the hydrofluoric acid and other components. Moreover, because the sulfonic acid provides the composition with a high viscosity when present with highly concentrated free acid even with a small addition of magnesium, it is possible to prepare a composition having a powerful effect as well as a desired viscosity for cleaning and for etching of metals.
  • nitric acid When nitric acid is employed as a component, its concentration is chosen in a range of from about 1% to about 70% weight. At a concentration of less than about 1%, the viscosity-increasing effect and the cleaning or etching are not sufficient. At a concentration of more than about 70%, the volatility of the nitric acid is too high, making the handling of the composition dangerous.
  • the concentration thereof ranges from about 1% to about by weight. At a concentration of less than about 1%, the viscosity-increasing effect and the cleaning or etching effect are not sufficient. At a concentration of more than about 90%, the cleaning or etching effect is lowered.
  • sulfuric acid When sulfuric acid is employed as a component, its concentration is chosen in a range of from about 0.1% to about 90% by weight. At a concentration of less than about 0.1%, the viscosity-increasing effect and the cleaning or etching effect are not suflicient. At a concentration of more than about 90%, the volatility becomes too high, again making the handling of the composition dangerous.
  • sulfonic acid When sulfonic acid is employed as a component, its concentration is chosen in a range of from about 0.1% to about 98% by weight, again based on the weight of the composition. At a concentration of less than about 0.1%, the viscosity-increasing effect is not suflicient. At a concentration of more than about 98%, the cleaning or etching effect and the viscosity-increasing effect are not sufficient.
  • the effects of the respective acids are as follows.
  • the nitric acid accelerates the solubility of smut which develops on the metal surface during the chemical reaction on the scale, thereby ensuring an even cleaning or etching.
  • the phosphoric acid prevents interangular corrosion, thereby moderating the action of the composition and preventing over-etching.
  • the sulfuric acid promotes cleaning, even with a small amount thereof.
  • the sulfonic acid removes oily stains and organic paints and coatings from the metal surface.
  • the composition of the present invention is prepared by selecting the kind and amount of said components in accordance with the intended use. For instance, in order to attain a strong cleaning or etching action, the hydrofluoric acid and other acid components which are effective in cleaning and etching are selected. Then, an appropriate amount of magnesium and an appropriate amount of a sulfonic acid which promotes the viscosity-increasing performance are added. These components are agitated together, thereby giving the desired composition. A small quantity of a surface-active agent may be added to the composition in order to promote the cleaning or etching effect. Also, an appropriate amount of an inhibitor may be added in order to prevent over-etching.
  • the composition of the present invention may be used after dilution with water so as to obtain a suitable viscosity, depending upon the intended use and the desired mode of application. The final composition has the appearance of a transparent or opaque jelly or cream.
  • the present invention is not to be limited by the veracity of any theoretical explanation thereof, it may be reasonably surmised that the substance which causes the viscosity in the composition is not a mere salt or mixture, but is perhaps a substance formed by a multiple combination with the addition of the hydrofluoric acid, magnesium and at least one of nitric acid, phosphoric acid, sulfuric acid, sulfonic acid and water, and that said multiple combined substance seems to be the cause of the colloidal nature of the composition.
  • the composition containing hydrofluoric acid, magnesium sulfate and water has a transparent and jelly-like appearance.
  • composition has a semitransparent and jelly-like appearance, and this is presumed to be caused by a formation of a colloidal substance different from any of the magnesium salts of the component acids, namely, hydrofluoric acid, sulfuric acid or propylnaphthayene-sulfonic acid.
  • the appropriate amount of magnesium required for obtaining a viscosity suitable for use can be made very small.
  • a simple composition consisting essentially of only hydrofluoric acid and magnesium is required to contain at least 9% of magnesium, when the compound contains 85% of hydrofluoric acid of 55% concentration, in order to attain a suitable viscosity. With any less content of magnesium, the viscosity is poor.
  • a composition of high viscosity can be obtained by a small addition of the magnesium.
  • the amount of the magnesium is only 0.6%.
  • the composition can be prepared with even a less amount of magnesium.
  • the viscosity of the composition in this invention is shown hereunder by means of a unit called the spread area, which exhibits the reverse value of the viscosity.
  • the spread area in this invention is defined as an area which is measured in the manner that cc. of a composition is dropped onto a horizontally placed smooth poly ethylene plate, from a nozzle having a round downward opening of 2 mm. diameter and placed 5 cm. above said polyethylene plate, at an even dropping rate for 20 seconds. Then, the area of the spread composition is measured after a lapse of 2 minutes from the finish of said dropping, the procedure being conducted at temperatures of 20 C. :1" C. By such measurement, the spread area of distilled water is 22.5 cm. and that of said simple hydrofiuoric acid-magnesium composition is 8.3 cmF, while that of the latter exemplary composition is 1.7 cm.
  • a conventional cleaning solution for stainless steel consisting of 5% of hydrofluoric acid of 55 concentration
  • the viscosity is large when the spread area is small, as is described above, and the composition is plastic like a jelly having no fluidity at all at a spread area of less than 3 cm. However, the composition becomes slightly more fluid and gains an appearance like a cream at a spread area of around 5 cm. and gains more fluidity at a spread area of over 10 cm.
  • the composition of the present invention exhibits a larger viscosity than said simple hydrofluoric acid-magnesium mixture. Moreover, the composition of the present invention has a colloidal appearance resembling a jelly or cream, and its viscosity can be widely selected in accordance with the intended use. Furthermore, the viscosity of the composition of the present invention remains stable, the composition exhibiting a good durability.
  • the composition of the invention also has the feature that a suflicient amount of active or free acid is stably retained therein, because only a small amount of magnesium is required and, therefore, a decrease of the active or free acid because of a large amount of magnesium and a resultant interference with the cleaning function do not take place.
  • This feature of the invention is derived from the necessary and suflicient condition of the composition comprising hydrofluoric acid, magnesium and at least one other additive selected from the group consisting of nitric acid, phosphoric acid, sulfuric acid and sulfonic acids. Especially, when a sulfonic acid is selected as an additive, a desired viscosity of the compound or composition of the invention can be obtained without lowering the cleaning function.
  • compositions having a cleaning or etching action, as well as a stable and sufficient viscosity suitable for the respective purposes in a wide range can be obtained because the requirements of the components for attaining the desired viscosity are flexible, and the components act to complement each other.
  • the mixtures consisting solely of inorganic substance components can be readily prepared with a quick attainment of chemical equilibrium, and they are stable for a long time without the occurrence of undesirable and unnecessary chemical changes or reactions during storage.
  • the compositions of the present invention containing sulfonic acid are also stable for a long time, because the sulfonic acid has a good stability which is a feature of aryl sulfonic acids, alkylaryl sulfonic acids and alkyl sulfonic acids, as contrasted with carbohydrates. Accordingly, the composition of the invention does not show a decrease of viscosity or a precipitation into the solid state of the component materials and, therefore, has a good durability.
  • compositions for cleaning and for etching metal surfaces can be obtained according to the present invention, ranging from those having high viscosities, i.e., having spread areas of less than 6 cm. which are suitable for application to vertical or overhanging surfaces, to those having low viscosities, i.e., having spread areas of more than 10 cm.
  • the spread area of this composition is 1.6 cm.
  • the spread area after storing the composition for 30 days at temperatures of 20 C.i1 C. is also 1.6 cm. there being no change at all.
  • This composition can remove welding scales on a 5 mm. thick plate of titanium [of Japanese Industrial Standard (hereinafter indicated JIS) H4600 TP28, namely containing Hzmax 0.0551; Oxnax 0.20%; Nrmax 0.05%; Fe:max 0.20% and having a tensile strength of 28 kg./mm. in 30 minutes, and no over-etching is observed.
  • JIS Japanese Industrial Standard
  • a composition prepared by adding 35% of water to the above-mentioned mixture has a transparent creamlike appearance and a spread area of 9.9 cm. and is capable of removing welding scales from a 1 mm. thick plate of titanium (of IIS TP49, namely containing H:max 0.05%; O:max 0.40%; Nzmax 0.07%; Fe:max 0.40% and having a tensile strength of 49 kg./mm. by an application for 5 to minutes.
  • the composition obtained by blending and reacting the above components has a spread area of 6.9 cm. and a cream-like appearance.
  • a fine satin-like etched surface can be obtained by applying this composition for 2 hours to an exposed part of stainless steel (of AISI 304) covered by parafiin wax, excepting an ornamental pattern.
  • the etching depth is about 0.3 mm.
  • Etching by this composition requires a smaller quantity of the composition; also there is no need of covering the whole part of the object matter with wax, because the etching can be done by applying the cream-like mixture only to a necessary limited part of the object matter, instead of immersing the whole part thereof. Moreover, an etching bath is not necessary and etching is even and line.
  • the composition obtained by blending and reacting the above component materials has a spread area of 1.6 cm. having almost no fluidity and showing a transparent cream-like appearance.
  • the spread area of this composition stored for 30 days at temperatures of C: 1 C. is also 1.6 cm.
  • the heat scales on a titanium plate (of 8 HS T1 49) of 1 mm. thickness can be removed by a 30 minute application of this composition.
  • the composition obtained by blending and reacting the above component materials has a spread area of 1.5 cm.
  • the spread area of this composition after storing for 30 days at temperatures of 20 C.:1 C. is 1.5 cm.
  • Arcwelding scales on a stainless steel plate (of AISI 304L) can be removed by application of this composition for 2-3 hours.
  • the composition obtained by blending and reacting the above components has a spread area of 1.6 cm. and after storing the compound for 30 days at temperatures of 20 C.;L-l C. the spread area is also 1.6 cm Arc-welding scales on a stainless steel (of AISI 304L) can be removed in 2 to 3 hours by application of this composition.
  • the spread area of the composition stored for 24 hours after preparation by blending and reacting the above component materials is 9.0 cm. and the spread area after storing the composition for 60 days at temperatures of 20 011 C. is 8.8 cm.
  • Heat scales on a heat-resisting steel (of A181 310) can be removed by applying this composition for 30 to minutes.
  • the spread area of the composition stored for 24 hours after preparation by blending and reacting the above component materials is 8.5 cm. and the spread area after storing the composition for 30 days at temperatures of 20 C.- l C. is 8.4 cm.
  • Heat scales on a heat-resisting steel (of A181 310) can be removed by application of this composition for less than 2 hours.
  • the spread area of the total composition stored for 24 hours after preparation by blending and reacting the above component materials is 1.6 cm. and the spread area after storing the composition for 60 days at temperatures of 20 Oil" C. is also 1.6 cm. showing no change.
  • Welding scales on a stainless steel (of AISI 316) can be cleaned by application of this composition for about 1 hour.
  • composition obtained by blending and reacting the above component materials has a spread area of 1.7 cmf and a transparent jelly-like appearance. Welding-scales on a stainless steel (of AlSiI 316) can be removed by application of this composition for 1 to 2 hours.
  • the composition of this example has the feature that the over-etching action is safely low.
  • the spread area of this compound mixture after storing for 6 months at normal temperatures is 1.7 cm. showing no change of viscosity.
  • the spread area of the composition obtained by blending and reacting the above component materials is 10.9 cm.
  • the spread area of this composition after storing for 30 days at temperatures of 20 C.i1 C. is 10.7 cm.
  • Heat scales on a stainless steel (of AISI 304) can be removed by applying this composition for 1 hour.
  • the composition obtained by blending and reacting the above component materials has almost a transparent jelly-like appearance and has a spread area of 1.7 cm.
  • This composition is suitable for removing corrosion, oxidation and stains on aluminum without over-etching.
  • a grayish-white corrosion, oxidation and stain on a plate of aluminum [of Aluminum Association of USA standard (hereinafter indicated AA) 1100] weather-tested outdoors for 6 months can be removed by applying this composition for to 30 minutes, recovering the white metallic luster of aluminum.
  • the spread area after storing for 6 months at ordinary temperature is 1.6 cm.
  • the composition obtained by blending and reacting the above component materials has a spread area of 10.4 cm.
  • the spread area after storing for 30 days at temperatures of 20 C.il C. is 10.2 cm.
  • Welding-scales on a steel plate [of the American Society of Testing and Material standard (hereinafter indicated ASTM) A366- 66T] can be removed by applying this composition for 60 minutes.
  • the composition has a mild character, and there is no over-etching.
  • the composition obtained by blending and reacting the above component materials has a spread area of 4.4 cm. and has a cream-like appearance.
  • the spread area after storing it for 30 days at temperatures of 20 C.:l C. is also 4.4 cm.
  • Scales on high silicon iron (containing 0.5% of carbon, 15.5% of silicon, 0.4% of manganese, 0.07% of phosphorus and 0.02% of sulfur) can be removed by applying this composition for 1 hour.
  • the composition obtained by blending and reacting the above component materials has a spread area of 1.7 cm. and the spread area after storing it for 6 months at normal (room) temperature is 1.6 cm. Welding-scales on stainless steel (of AISI 304) can be removed by applying this composition for 2 hours.
  • the composition obtained by blending and reacting the above component materials has a spread area of 5.1 cm. and a cream-like appearance. Welding-scales on stainless steel (of AISI 304) can be removed in 1 to 2 hours by application of this composition. The spread area after storing it for 3 months at normal temperature is 5.2 cm.
  • composition prepared by adding 1% of potassium sulfate can remove said scales in a time that is shorter than with the above composition, and it exhibits a spread area of 5.0 cm. right after its preparation as well as after storing it for 3 months at normal temperatures.
  • the composition or compound of the present invention can clean a metal surface, as well as etch a metal surface, because the cleaning operation is a combination of removing non-metallic deposits from the metal surface and a slight etching of the surface of the metal.
  • a composition for etching and cleaning metal surfaces comprising hydrofluoric acid, magnesium and at least one acid or salt of an acid selected from the group consisting of nitric acid, phosphoric acid, sulfuric acid and sulfonic acids having the formula XSO H, wherein X is an aryl, alkaryl or alkyl radical.
  • composition according to claim 1 wherein the sulfonic acid is an aryl or alkaryl sulfonic acid containing up to 28 carbon atoms.
  • composition according to claim 1 wherein the sulfonic acid is dodecylbenzene sulfonic acid.
  • composition according to claim 1 wherein the sulfonic acid is an alkyl sulfonic acid containing from 6 to 30 carbon atoms.
  • a composition for etching and cleaning metal sur- 12 faces comprising hydrofluoric acid, magnesium and at least one acid or salt of an acid selected from the group consisting of sulfonic acids having the formula XSO H, wherein X is an aryl, alkaryl or alkyl radical.
  • composition according to claim 5 wherein X is an aryl or alkaryl radical containing up to 28 carbon atoms.
  • a composition for etching and cleaning metal surfaces comprising hydrofluoric acid, magnesium and at least one acid or salt of an acid selected from the group consisting of sulfonic acids having the formula XSO H, wherein X is an aryl, alkaryl or alkyl radical, and at least one member selected from the group consisting of nitric acid, phosphoric acid, sulfuric acid and salts thereof.
  • a composition for etching and cleaning metal surfaces comprising about 165% by weight of hydrofluoric acid, about 01-20% by weight of magnesium and at least one acid or salt of an acid selected from the group consisting of about 1-70% by weight of nitric acid, about l-% by weight of phosphoric acid, about 01-90% by weight of a sulfuric acid and about 01-98% by weight of a sulfonic acid having the formula XSO H, wherein X is an aryl, alkaryl or alkyl radical.
  • composition according to claim 9 wherein the sulfonic acid is selected from the group consisting of aryl or alkaryl sulfonic acids of up to 28 carbon atoms and alkyl sulfonic acids of 6 to 30 carbon atoms.
  • composition according to claim 9 wherein the sulfonic acid is dodecylbenzene sulfonic acid.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
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US864535A 1968-10-07 1969-10-07 Acid compound for metal surface Expired - Lifetime US3598741A (en)

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JP7302368 1968-10-07
JP43073022A JPS4942775B1 (de) 1968-10-07 1968-10-07

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DE (1) DE1950560C3 (de)
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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804689A (en) * 1971-12-03 1974-04-16 Ncr Process for removing copper films from substrates
US3844859A (en) * 1969-12-16 1974-10-29 Boeing Co Titanium chemical milling etchant
US3905907A (en) * 1972-12-22 1975-09-16 Furukawa Electric Co Ltd Solutions for chemical dissolution treatment of metal materials
US4002489A (en) * 1973-06-21 1977-01-11 Nyby Bruk Ab Method of pickling metallic material
US4165295A (en) * 1976-10-04 1979-08-21 Allied Chemical Corporation Organic stripping compositions and method for using same
US4215005A (en) * 1978-01-30 1980-07-29 Allied Chemical Corporation Organic stripping compositions and method for using same
EP0019752A1 (de) * 1979-05-25 1980-12-10 Deutsche Derustit GmbH Verfahren zum Beizen von Metallen
US4314855A (en) * 1979-12-17 1982-02-09 Bell Telephone Laboratories, Incorporated Method of cleaning test probes
EP0058257A1 (de) * 1981-02-14 1982-08-25 Metallgesellschaft Ag Beiz- und Entrostungspaste für Metalle
FR2527642A1 (fr) * 1982-05-25 1983-12-02 Cezus Co Europ Zirconium Procede d'usinage chimique de metaux
US4432808A (en) * 1982-05-26 1984-02-21 Textron Inc. Treatment of stainless steel apparatus used in the manufacture, transport or storage of nitrogen oxides
US4581102A (en) * 1984-08-20 1986-04-08 Olin Corporation Copper-base alloy cleaning solution
DE3530132A1 (de) * 1985-08-23 1987-02-26 August Wittig Oberflaechen beiz- und entrostungspaste zum reinigen von metalloberflaechen insbesondere aus edelstahl und/oder aluminium u. aluminiumlegierungen
US4902351A (en) * 1981-11-02 1990-02-20 Kernforschungszentrum Karlsruhe Gmbh Method for decontaminating radioactively contaminated surfaces of metallic materials
US5275696A (en) * 1993-05-03 1994-01-04 The United States Of America As Represented By The Secretary Of The Navy Stainless steel surface treatment
US5439553A (en) * 1994-03-30 1995-08-08 Penn State Research Foundation Controlled etching of oxides via gas phase reactions
WO1995035397A1 (en) * 1994-06-17 1995-12-28 Ta Chemistry Ab Process for stainless steel pickling
WO2001053567A1 (en) * 2000-01-19 2001-07-26 Avestapolarit Aktiebolag (Publ) Pickling agent containing urea and method of producing it
EP1674561A1 (de) * 2004-12-27 2006-06-28 General Electric Company Verfahren zur Entfernung von Maschinenablagerungen von Turbinenbauteilen und dafür zuverwendende Zusammensetzung
WO2006061741A3 (en) * 2004-12-06 2008-01-17 Koninkl Philips Electronics Nv Etchant solutions and additives therefor
US7699936B2 (en) 2003-08-11 2010-04-20 Gm Global Technology Operations, Inc. Composition and method for surface treatment of oxidized metal
US20110159636A1 (en) * 2008-09-01 2011-06-30 Merck Patent Gesellschaft Mit Beschrankter Haftung Edge deletion of thin-layer solar modules by etching
US20160024444A1 (en) * 2014-07-28 2016-01-28 United Technologies Corporation Gel solvent and method of removing diffusion and overlay coatings in gas turbine engines
EP3991862A1 (de) * 2017-06-13 2022-05-04 General Electric Company System und verfahren zur selektiven reinigung von turbinenmotorkomponenten

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19833990A1 (de) 1998-07-29 2000-02-10 Metallgesellschaft Ag Beizmittel für Edelstähle

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844859A (en) * 1969-12-16 1974-10-29 Boeing Co Titanium chemical milling etchant
US3804689A (en) * 1971-12-03 1974-04-16 Ncr Process for removing copper films from substrates
US3905907A (en) * 1972-12-22 1975-09-16 Furukawa Electric Co Ltd Solutions for chemical dissolution treatment of metal materials
US4002489A (en) * 1973-06-21 1977-01-11 Nyby Bruk Ab Method of pickling metallic material
US4165295A (en) * 1976-10-04 1979-08-21 Allied Chemical Corporation Organic stripping compositions and method for using same
US4215005A (en) * 1978-01-30 1980-07-29 Allied Chemical Corporation Organic stripping compositions and method for using same
EP0019752A1 (de) * 1979-05-25 1980-12-10 Deutsche Derustit GmbH Verfahren zum Beizen von Metallen
US4314855A (en) * 1979-12-17 1982-02-09 Bell Telephone Laboratories, Incorporated Method of cleaning test probes
EP0058257A1 (de) * 1981-02-14 1982-08-25 Metallgesellschaft Ag Beiz- und Entrostungspaste für Metalle
US4902351A (en) * 1981-11-02 1990-02-20 Kernforschungszentrum Karlsruhe Gmbh Method for decontaminating radioactively contaminated surfaces of metallic materials
FR2527642A1 (fr) * 1982-05-25 1983-12-02 Cezus Co Europ Zirconium Procede d'usinage chimique de metaux
US4432808A (en) * 1982-05-26 1984-02-21 Textron Inc. Treatment of stainless steel apparatus used in the manufacture, transport or storage of nitrogen oxides
US4581102A (en) * 1984-08-20 1986-04-08 Olin Corporation Copper-base alloy cleaning solution
DE3530132A1 (de) * 1985-08-23 1987-02-26 August Wittig Oberflaechen beiz- und entrostungspaste zum reinigen von metalloberflaechen insbesondere aus edelstahl und/oder aluminium u. aluminiumlegierungen
US5275696A (en) * 1993-05-03 1994-01-04 The United States Of America As Represented By The Secretary Of The Navy Stainless steel surface treatment
USRE38760E1 (en) 1994-03-30 2005-07-19 Penn State Research Foundation Controlled etching of oxides via gas phase reactions
US5439553A (en) * 1994-03-30 1995-08-08 Penn State Research Foundation Controlled etching of oxides via gas phase reactions
WO1995035397A1 (en) * 1994-06-17 1995-12-28 Ta Chemistry Ab Process for stainless steel pickling
KR100749600B1 (ko) 2000-01-19 2007-08-14 아베스타 웰딩 악티에보라그 요소를 함유하는 산세제 및 그 제조 방법
US6844304B2 (en) 2000-01-19 2005-01-18 Avestapolarit Aktiebolag (Publ) Pickling agent containing urea and method of producing it
WO2001053567A1 (en) * 2000-01-19 2001-07-26 Avestapolarit Aktiebolag (Publ) Pickling agent containing urea and method of producing it
US7699936B2 (en) 2003-08-11 2010-04-20 Gm Global Technology Operations, Inc. Composition and method for surface treatment of oxidized metal
WO2006061741A3 (en) * 2004-12-06 2008-01-17 Koninkl Philips Electronics Nv Etchant solutions and additives therefor
US20110104840A1 (en) * 2004-12-06 2011-05-05 Koninklijke Philips Electronics, N.V. Etchant Solutions And Additives Therefor
EP1674561A1 (de) * 2004-12-27 2006-06-28 General Electric Company Verfahren zur Entfernung von Maschinenablagerungen von Turbinenbauteilen und dafür zuverwendende Zusammensetzung
US20110159636A1 (en) * 2008-09-01 2011-06-30 Merck Patent Gesellschaft Mit Beschrankter Haftung Edge deletion of thin-layer solar modules by etching
US8497215B2 (en) * 2008-09-01 2013-07-30 Merck Patent Gmbh Edge deletion of thin-layer solar modules by etching
US20160024444A1 (en) * 2014-07-28 2016-01-28 United Technologies Corporation Gel solvent and method of removing diffusion and overlay coatings in gas turbine engines
EP3991862A1 (de) * 2017-06-13 2022-05-04 General Electric Company System und verfahren zur selektiven reinigung von turbinenmotorkomponenten
US11578613B2 (en) 2017-06-13 2023-02-14 General Electric Company System and methods for selective cleaning of turbine engine components

Also Published As

Publication number Publication date
DE1950560A1 (de) 1970-04-23
GB1279834A (en) 1972-06-28
DE1950560C3 (de) 1979-09-06
DE1950560B2 (de) 1979-01-04

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